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Catalytic Synthesis of Hydroxymethyl‐2‐oxazolidinones from Glycerol or Glycerol Carbonate and Urea
Author(s) -
Dibenedetto Angela,
Nocito Francesco,
Angelini Antonella,
Papai Imre,
Aresta Michele,
Mancuso Raffaella
Publication year - 2013
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201200524
Subject(s) - glycerol , chemistry , moiety , urea , selectivity , carbonate , catalysis , hydroxymethyl , yield (engineering) , polyol , inorganic chemistry , nuclear chemistry , organic chemistry , materials science , metallurgy , polyurethane
Oxazolidinones have been synthesized by reacting glycerol carbonate or glycerol with urea in the presence of γ‐Zr phosphate as a catalyst. The conversion yield of the polyol or its carbonate depends on the temperature. Below 408 K the selectivity is 100 % with a conversion of up to 25 %, whereas increasing the temperature means that conversion yield grows, but the selectivity decreases, which makes the separation process more difficult. Starting from glycerol carbonate, two isomers, 6 and 6′ , are formed with a quasi 1:1 molar ratio because urea can attack the carbonate moiety on both sides of the carboxylic CO moiety. From glycerol the formation of the 6 ′ isomer is preferred: the ratio of 6′ / 6 is close to 7. The oxazolidinones formed act as templates because they interact through hydrogen bonding with glycerol. The intensity of the interaction depends on the 6 or 6′ isomer: DFT calculations showed that the energy was 22.6 kcal mol −1 for 6 ‐oxazolidinone and 25.7 kcal mol −1 for 6′ ‐oxazolidinone.